WO2012120926A1 - 炭化水素燃料の製造方法 - Google Patents
炭化水素燃料の製造方法 Download PDFInfo
- Publication number
- WO2012120926A1 WO2012120926A1 PCT/JP2012/051126 JP2012051126W WO2012120926A1 WO 2012120926 A1 WO2012120926 A1 WO 2012120926A1 JP 2012051126 W JP2012051126 W JP 2012051126W WO 2012120926 A1 WO2012120926 A1 WO 2012120926A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aliphatic compound
- temperature
- aliphatic
- hydrocarbon
- catalyst
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/10—Production of fats or fatty oils from raw materials by extracting
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
- C11B7/0008—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents
- C11B7/0016—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents in hydrocarbons or halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the present invention relates to a method for producing a hydrocarbon fuel.
- a solvent extraction method using a solvent having a high solubility of an aliphatic compound such as hexane or ethyl acetate and extracting at a temperature below the boiling point of the solvent under normal pressure is widely used.
- the aliphatic compounds produced by algae are poor in fluidity because they are straight-chain molecules, and when the aliphatic compounds are fats and oils, the content of oxygen is high, which adversely affects engine materials. In other words, the quality of the fuel is low. Therefore, in order to obtain high-quality fuel from aliphatic compounds produced by algae, hydrodeoxygenation treatment, hydrocracking treatment, hydroisomerization treatment, etc. are performed on the aliphatic compounds using a catalyst. By performing a hydrogenation treatment, it is necessary to change the structure of the aliphatic compound, such as removal of oxygen content, reduction in molecular weight, or introduction of a branched chain.
- the present invention has been made in view of such circumstances, and is capable of producing a hydrocarbon fuel that can stably produce a high-quality hydrocarbon fuel commercially from an aliphatic compound produced by algae. It aims to provide a method.
- the present invention provides a mixture containing an aliphatic compound produced by algae and a hydrocarbon solvent having a critical temperature in a supercritical state of 90 ° C. or higher.
- the hydrocarbon fuel production method of the present invention has the above-described configuration, deactivation of the catalyst can be sufficiently suppressed during the hydrotreatment in the second step, and high-quality hydrocarbon fuel is commercially available. Therefore, it can be manufactured stably.
- the present inventors guess as follows about the reason which said effect is show
- Mg magnesium
- Na sodium
- a mixture containing an aliphatic compound produced by algae and a hydrocarbon solvent having a critical temperature in a supercritical state of 90 ° C. or higher is aliphatic.
- the solubility of the compound in the hydrocarbon solvent is 15 g or less per 100 g of the hydrocarbon solvent
- the soluble component of the aliphatic compound in the hydrocarbon solvent is recovered, It is possible to sufficiently prevent the metal component from being mixed into the recovered aliphatic compound. And it is guessed that poisoning and deactivation of the catalyst by a metal part can fully be suppressed by using the aliphatic compound collect
- the algae may include at least one selected from the group consisting of Chlorella, Icadamo, Arthrospira, Euglena, Botryococcus and Pseudocollistis. preferable.
- a method for producing a hydrocarbon fuel capable of commercially stably producing a high quality hydrocarbon fuel from an aliphatic compound recovered from algae.
- a mixture containing an aliphatic compound produced by algae and a hydrocarbon solvent having a critical temperature of 90 ° C. or higher is used as a hydrocarbon solvent for the aliphatic compound.
- the temperature and pressure are adjusted and maintained above the critical temperature of the hydrocarbon solvent so that the solubility is 15 g or less per 100 g of the hydrocarbon solvent, and then the soluble component of the aliphatic compound in the hydrocarbon solvent is recovered.
- a second step of hydrotreating the soluble component recovered in the first step using a catalyst is
- the effect of the present invention can be obtained at a temperature at which the mixture of the aliphatic compound produced by algae and the hydrocarbon solvent having a critical temperature of 90 ° C. or higher is lower than the critical temperature of the hydrocarbon solvent. Have difficulty. Moreover, when the solubility of the aliphatic compound in the hydrocarbon solvent at the holding temperature of the mixture exceeds 15 g per 100 g of the hydrocarbon solvent, it is difficult to obtain the effects of the present invention.
- the solubility of the aliphatic compound in the hydrocarbon solvent at the above holding temperature is preferably 10 g or less, particularly preferably 6 g or less, per 100 g of the hydrocarbon solvent. Further, from the viewpoint of processing efficiency (recovery efficiency of purified aliphatic compound), the solubility of the aliphatic compound in the hydrocarbon solvent at the holding temperature is preferably 1 g or more per 100 g of the hydrocarbon solvent.
- the aliphatic compounds produced by algae which are the raw materials for hydrocarbon fuels, include fats and oils, aliphatic hydrocarbons and the like.
- the algae producing an aliphatic compound refers to an organism (algae) living in water that performs oxygen-generating photosynthesis and that produces an aliphatic compound in the body. Algae has the property of fixing carbon dioxide by photosynthesis and converting it into aliphatic compounds. Any algae that have such properties can be used in the method for producing an aliphatic compound of the present embodiment.
- Examples of algae that produce an aliphatic compound in the present embodiment include algae belonging to the genus Chlorella, Ikadamo, Arsulospira, Euglena, Botriococcus, and Pseudocollistis. More specifically, chlorella, squid damo, spirulina, euglena, Botriococcus brownie, pseudocollistis ellipsoidia and the like can be mentioned. However, algae are not limited to these as long as they produce aliphatic compounds.
- chlorella, squid damo, spirulina, and euglena produce fats and oils
- Botriococcus brownie and pseudocollistis ellipsoidia produce aliphatic hydrocarbons.
- These aliphatic compounds are usually accumulated in algal cells (algae), but in the culturing step, some of the aliphatic compounds accumulated in the cells may be discharged out of the cells.
- Examples of fats and oils produced by cultured algae include aliphatic ester compounds composed of aliphatic carboxylic acids and monovalent or trivalent aliphatic alcohols.
- the oil and fat is not particularly limited as long as it is produced by algae, and examples thereof include methyl laurate, myristyl myristate, and methyl palmitate.
- Aliphatic hydrocarbons produced by cultured algae include solid and liquid aliphatic hydrocarbons composed of carbon atoms and hydrogen atoms, for example, saturated or unsaturated aliphatic hydrocarbons having 15 to 40 carbon atoms. There may be mentioned hydrocarbons, in particular linear aliphatic hydrocarbons.
- the aliphatic hydrocarbon is not particularly limited as long as it is produced by algae, and examples thereof include n-heptadecene, n-eicosadiene and the like.
- each algae can be cultured under known culture conditions. Usually, it is cultured at normal temperature, preferably 25-37 ° C., by photoautotrophic culture in which algae are grown by photosynthesis using carbon dioxide in the air as a carbon source. As a light source for photosynthesis, sunlight or an artificial light source can be used. In order to accelerate the growth of the algae, the light irradiation to the algae is preferably performed at 2 to 100 kilolux for 30 to 500 hours. The concentration of carbon dioxide in the medium atmosphere is preferably 0.3 to 10% by volume. In order to promote the dissolution of carbon dioxide into the medium, the medium may be agitated or aerated with air as necessary. Good.
- a general inorganic medium such as a CHU medium, a JM medium, or an MDM medium can be used.
- the inorganic medium usually contains Ca (NO 3 ) 2 .4H 2 O or KNO 3 as a nitrogen source, and KH 2 PO 4 or MgSO 4 .7H 2 O as other main nutrient components.
- Antibiotics that do not affect the growth of algae may be added to the medium.
- the pH of the medium is preferably 3-10.
- the culture period depends on the amount of algal bodies inoculated first, it is preferably 1 to 20 days when the culture is started at an algal body concentration of 0.5 g / L. If the culture period is less than 1 day, a sufficient amount of algal bodies tends to be difficult to obtain, and if it exceeds 20 days, nutrients in the medium tend to be depleted and growth of algae tends to be difficult.
- the algal body concentration in the medium after completion of the culture is usually 0.01 to 3% by mass, although it varies depending on the type of algae and the culture conditions.
- the culture medium containing the aliphatic compound after culturing may be used as it is, or the culture medium is subjected to centrifugation or the like to provide algae. You may use what concentrated the body.
- the concentration of algal bodies when concentration is performed is usually 1 to 30% by weight.
- a dried alga body containing an aliphatic compound obtained by drying a medium or a concentrated solution thereof can also be used.
- algae extracted from algal bodies by a solvent extraction method using a solvent having a high solubility of aliphatic compounds such as hexane and ethyl acetate and extracting at a temperature below the boiling point of the solvent under normal pressure.
- a solvent having a high solubility of aliphatic compounds such as hexane and ethyl acetate
- An oil containing an aliphatic compound can also be used.
- the step of increasing the concentration of the aliphatic compound in the algal bodies can be performed as an intermediate step as necessary.
- this step for example, an operation of placing the medium containing algal bodies obtained by the culturing step or a concentrated solution thereof in an anaerobic state can be exemplified.
- the hydrocarbon solvent having a critical temperature of 90 ° C. or higher an aliphatic hydrocarbon having 3 to 6 carbon atoms is preferable.
- propane, n-butane, isobutane, n-pentane, n-hexane and the like are used. Can be mentioned. Among these, propane, n-butane, and isobutane are more preferable, and propane is particularly preferable.
- Table 1 shows the critical temperature and critical pressure of the hydrocarbon solvent.
- gravity sedimentation separation As a method for recovering the soluble component of the aliphatic compound in the hydrocarbon solvent, for example, gravity sedimentation separation can be used.
- the soluble component recovered in the first step is subjected to a hydrogenation treatment using a catalyst.
- the hydrotreating using a catalyst means performing at least one of hydrodeoxygenation, hydrocracking, and hydroisomerization using a catalyst.
- oxygen atoms contained in raw materials that may adversely affect engine materials are removed as water and / or alcohol, etc., and unsaturated bonds in the raw materials are hydrogenated to produce saturated fat.
- unsaturated bonds in the raw materials are hydrogenated to produce saturated fat.
- hydrocarbons By this hydrodeoxygenation treatment, it is possible to obtain a hydrocarbon fuel that does not substantially contain oxygen atoms and unsaturated bonds and is free of concerns such as engine damage.
- the aliphatic compound is an oil or fat (an ester composed of a fatty acid and glycerin), since it contains many oxygen atoms in its molecule, it is first subjected to hydrodeoxygenation treatment to remove oxygen atoms. It is preferable to remove. At the same time, when the oil or fat has an unsaturated bond in its molecule, the unsaturated bond is hydrogenated during hydrodeoxygenation treatment to produce a linear saturated hydrocarbon (normal paraffin).
- the generated normal paraffin is at least partially hydrotreated by the action of the catalyst. In some cases, it may be converted to normal paraffin having a lower carbon number after being decomposed. In addition, at least a part of the normal paraffin may be hydroisomerized and converted to a branched saturated hydrocarbon (isoparaffin) by the action of a catalyst.
- hydrocracking treatment saturated or unsaturated aliphatic hydrocarbons are converted into aliphatic hydrocarbons having a lower carbon number.
- the hydrocracking product generally has a lower molecular weight than the aliphatic hydrocarbon that is the raw material of the treatment, and at least a part thereof is generally an isoparaffin having a branched chain structure.
- the aliphatic compound When the aliphatic compound is a linear aliphatic hydrocarbon, it is waxy at room temperature as it is, and it is often difficult to use it as a liquid fuel. Moreover, even if this linear aliphatic hydrocarbon is liquid at room temperature, it has poor fluidity at low temperature. Therefore, by hydrocracking, straight-chain aliphatic hydrocarbons are converted into hydrocarbons having a smaller carbon number, and at the same time, at least a part thereof is converted into a branched structure by hydroisomerization, and at room temperature. It is preferably a liquid and has improved fluidity at low temperatures. Further, when the linear aliphatic hydrocarbon as the aliphatic compound has an unsaturated bond, the unsaturated bond is hydrogenated and converted into a saturated hydrocarbon during the hydrocracking treatment.
- the aliphatic compound is an oil and fat
- the process of converting the oil and fat into a saturated aliphatic hydrocarbon by hydrodeoxygenation in parallel with hydrodeoxygenation, hydrocracking and / or
- the produced saturated aliphatic hydrocarbon may be solid at room temperature, and even if it is liquid at room temperature, low-temperature fluidity may not be sufficient.
- a liquid hydrocarbon fuel that is liquid at normal temperature and excellent in low-temperature fluidity can be obtained.
- the obtained hydrocracked product is fractionated into fractions for each boiling range by means such as distillation, if necessary.
- the separated aliphatic hydrocarbons are used for various purposes as base materials for gasoline engines, heating (kerosene), jet engines, diesel engines, and the like.
- the linear fatty acid that is an aliphatic compound Hydrocarbons with a relatively small number of carbons in the aromatic hydrocarbon or when the aliphatic hydrocarbon is an oil and fat and the low-temperature fluidity of the saturated aliphatic hydrocarbon obtained by hydrodeoxygenation is not sufficient. Processing can be performed.
- the fuel substrate thus obtained is preferably used for jet engines and diesel engines.
- hydrodeoxygenation process hydrocracking process
- hydroisomerization process hydroisomerization process
- Examples of the catalyst used in the hydrodeoxygenation treatment include hydrodehydration of fats and oils derived from animals and plants as disclosed in, for example, JP 2010-121071, JP 2007-308564, JP 2007-308565, and the like.
- Catalysts used for oxygen treatment can be used. That is, the elements of Groups 6 and 8 to 10 of the periodic table are added to a support made of a porous inorganic oxide containing at least one element selected from aluminum, silicon, zirconium, boron, titanium and magnesium.
- a catalyst supporting at least one metal having a hydrogenation activity selected from (active metal) can be used.
- the “periodic table” means a periodic table of long-period elements defined by IUPAC (International Union of Pure and Applied Chemistry).
- the carrier examples include alumina, silica, zirconia, boria, titania, magnesia or a composite oxide formed by combining these, silica alumina, silica zirconia, alumina boria, silica titania, silica magnesia, and the like. .
- composite alumina such as silica alumina, silica zirconia, alumina boria, silica titania, silica magnesia and the like are preferable.
- the carrier may contain zeolite.
- carrier may contain binders, such as an alumina, a silica, a titania, a magnesia, in order to improve a moldability and mechanical strength.
- the active metal examples include molybdenum (Mo) and tungsten (W) as Group 6 metals, ruthenium (Ru) and osmium (Os) as Group 8 metals, and cobalt (Co) as Group 9 metals.
- Mo molybdenum
- Ru ruthenium
- Os osmium
- Co cobalt
- iridium (Ir) examples include nickel (Ni), palladium (Pd), and platinum (Pt).
- These metals may be used individually by 1 type, and may be used in combination of 2 or more type. Preferable examples in which two or more are used in combination include combinations of Ni—Mo, Co—Mo, Ni—Co—Mo, Ni—W, and the like.
- the catalyst is pretreated (preliminary) with a fluid containing a sulfur compound such as dimethyldisulfide before the catalyst is subjected to hydrodeoxygenation treatment. It is preferable to add a small amount of a sulfur compound to the feed oil during the treatment.
- a noble metal such as Pt, Pd, Rh is preferable.
- the noble metal is poisoned by a sulfur compound, and therefore, it is generally not subjected to preliminary sulfidation, but is subjected to a reduction treatment with hydrogen gas or the like and subjected to a hydrodeoxygenation treatment.
- a noble metal for example, Pt—Pd or a combination of two or more kinds may be used.
- the supported amount based on the total mass of the active metal carrier is 0.1 to 3% by mass as a metal atom when the active metal is a noble metal, and 2 as a metal oxide when the active metal is a metal other than a noble metal. It is preferably ⁇ 50% by mass.
- the method for supporting the active metal on the carrier is not particularly limited, and a known method applied when producing a normal hydrodesulfurization catalyst or the like can be used.
- a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
- an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are preferably employed.
- the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.
- the reactor type for the hydrodeoxygenation treatment may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the raw material oil, or a combination of countercurrent and cocurrent flow having a plurality of reaction towers. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Further, the reactors may be used singly or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
- the treatment conditions in the hydrodeoxygenation treatment are preferably a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁇ 1 , a hydrogen / oil ratio of 150 to 1500 NL / L, and a hydrogen pressure of More preferably, it is 2 to 13 MPa, the liquid space velocity is 0.1 to 3.0 h ⁇ 1 , the hydrogen / oil ratio is 150 to 1500 NL / L, the hydrogen pressure is 3 to 10.5 MPa, and the liquid space velocity is 0.1.
- the conditions of 25 to 1.0 h ⁇ 1 and a hydrogen / oil ratio of 300 to 1000 NL / L are particularly preferred.
- the treatment temperature is generally preferably in the range of 150 to 480 ° C., preferably 200 to 400 ° C., more preferably 260 to 360 ° C. as the average temperature of the entire reactor.
- the reaction temperature is less than 150 ° C, the reaction may not proceed sufficiently.
- the reaction temperature exceeds 480 ° C, the decomposition proceeds excessively, and the product yield tends to decrease.
- hydrodeoxygenation treatment involves generation of a large reaction heat
- a known catalyst used for the hydrocracking treatment of hydrocarbons containing a wax component can be used. That is, a carrier containing a solid acid and carrying a metal belonging to Groups 8 to 10 of the periodic table as an active metal can be mentioned.
- Suitable supports include crystalline zeolites such as ultra-stable Y-type (USY) zeolite, Y-type zeolite, mordenite and beta zeolite, and amorphous composite metals having fire resistance such as silica alumina, silica zirconia, and alumina boria. What is comprised including 1 or more types of solid acids chosen from an oxide is mentioned. Further, the carrier is more preferably composed of USY zeolite and at least one solid acid selected from silica alumina, alumina boria and silica zirconia. USY zeolite, alumina boria and / or silica More preferably, it contains alumina.
- USY zeolite, alumina boria and / or silica More preferably, it contains alumina.
- USY zeolite is obtained by ultra-stabilizing Y-type zeolite by hydrothermal treatment and / or acid treatment, and in addition to a micropore structure called micropores having a pore size originally possessed by Y-type zeolite of 2 nm or less. New pores having a pore diameter in the range of 10 nm are formed.
- the average particle size of the USY zeolite is not particularly limited, but is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the silica / alumina molar ratio is preferably 10 to 200, more preferably 15 to 100, and further preferably 20 to 60.
- the carrier is preferably composed of 0.1 to 80% by mass of crystalline zeolite and 0.1 to 60% by mass of amorphous composite metal oxide having fire resistance.
- the carrier can be produced by molding a carrier composition containing the solid acid and, if necessary, a binder, followed by firing.
- the blending ratio of the solid acid is preferably 1 to 70% by mass, more preferably 2 to 60% by mass based on the total amount of the carrier.
- the carrier is configured to contain USY zeolite, the blending ratio of USY zeolite is preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass based on the mass of the entire carrier. It is more preferable.
- the mixing ratio of USY zeolite and alumina boria is preferably 0.03 to 1 in terms of mass ratio.
- the blending ratio of USY zeolite to silica alumina is preferably 0.03 to 1 in terms of mass ratio.
- the binder is not particularly limited, but alumina, silica, titania and magnesia are preferable, and alumina is more preferable.
- the blending amount of the binder is preferably 20 to 98% by mass, more preferably 30 to 96% by mass based on the mass of the whole carrier.
- the shape of the molded carrier is not limited, and examples thereof include a spherical shape, a cylindrical shape, and a deformed cylindrical shape having a trefoil / four-leaf cross section.
- the particle diameter is not particularly limited, but is preferably 1 ⁇ m to 10 mm in view of practicality.
- the firing temperature of the carrier composition is preferably in the range of 400 to 550 ° C., more preferably in the range of 470 to 530 ° C., and still more preferably in the range of 490 to 530 ° C.
- metals in Groups 8 to 10 of the periodic table include cobalt, nickel, rhodium, palladium, iridium, and platinum. Among these, it is preferable to use the metal chosen from nickel, palladium, and platinum individually by 1 type or in combination of 2 or more types. These metals can be supported on the above-mentioned carrier by a conventional method such as impregnation or ion exchange.
- the amount of metal to be supported is not particularly limited, but the total amount of metal is preferably 0.1 to 3.0% by mass with respect to the mass of the carrier.
- a catalyst used for hydroisomerization treatment a catalyst generally used for hydroisomerization in petroleum refining or the like, that is, a catalyst in which an active metal having a hydrogenating ability is supported on an inorganic carrier can be used. .
- the inorganic carrier constituting the catalyst examples include metal oxides such as alumina, silica, titania, zirconia, and boria. These metal oxides may be one kind or a mixture of two or more kinds or a composite metal oxide such as silica alumina, silica zirconia, alumina zirconia, alumina boria and the like.
- the inorganic carrier is preferably a complex metal oxide having solid acidity such as silica alumina, silica zirconia, alumina zirconia, alumina boria, etc., from the viewpoint of allowing hydroisomerization to proceed efficiently.
- the inorganic carrier may contain a small amount of zeolite.
- the inorganic carrier may contain a binder for the purpose of improving the moldability and mechanical strength of the carrier.
- Preferred binders include alumina, silica, magnesia and the like.
- one or more metals selected from the group consisting of Group 8 to Group 10 metals are used as the active metal constituting the catalyst.
- these metals include noble metals such as platinum, palladium, rhodium, ruthenium, iridium and osmium, or cobalt and nickel, preferably platinum, palladium, nickel and cobalt, and more preferably Are platinum and palladium.
- noble metals such as platinum, palladium, rhodium, ruthenium, iridium and osmium, or cobalt and nickel, preferably platinum, palladium, nickel and cobalt, and more preferably Are platinum and palladium.
- These metals are also preferably used in combination of a plurality of types. In this case, a preferable combination includes platinum-palladium and the like.
- the content of the active metal in the catalyst is preferably about 0.1 to 3% by mass as a metal atom based on the mass of the support when the active metal is the above-mentioned noble metal. Further, when the active metal is a metal other than the above-mentioned noble metals, the metal oxide is preferably about 2 to 50% by mass based on the mass of the support.
- the hydrodeoxygenation treatment, hydrocracking treatment, and hydroisomerization treatment described above may be performed by providing different steps, and by using a catalyst having a plurality of functions in one step.
- a plurality of processes may be performed simultaneously.
- hydrocracking not only the decomposition of the molecules constituting the feedstock but also the provision of branched chains by hydroisomerization usually proceeds simultaneously.
- a plurality of different catalyst beds may be provided in one reactor, and different treatments may be performed in each catalyst bed.
- a mixture containing an aliphatic compound such as fat or aliphatic hydrocarbon produced by algae and a hydrocarbon solvent having a critical temperature of 90 ° C. or more is obtained, and the carbonization of the aliphatic compound is performed on the mixture.
- the temperature and pressure are adjusted above the critical temperature of the hydrocarbon solvent so that the solubility in the hydrogen solvent is 15 g or less per 100 g of the hydrocarbon solvent, and the soluble component of the aliphatic compound in the hydrocarbon is recovered.
- High quality from the aliphatic compound produced by algae by making the first step and the second step of hydrotreating the soluble component obtained in the first step using a catalyst as essential steps This hydrocarbon fuel can be produced commercially stably.
- the aliphatic compound extraction separation tank 1, the solvent separation tank 2, and the hydrotreatment reactor 3 are arranged in this order from the upstream side.
- the aliphatic compound extraction / separation tank 1 and the solvent separation tank 2 are connected via a line L4, and the solvent separation tank 2 and the hydrotreating reactor 3 are connected via lines L6 and L7.
- a line L1 is connected to the upstream side of the aliphatic compound extraction / separation tank 1, and a pump 11, a mixing device 12, and a temperature adjusting device 13 are provided in this order from the upstream side.
- a plunger pump can be exemplified as the pump 11, a line mixer can be exemplified as the mixing device 12, and a heater using steam can be exemplified as the temperature adjusting device 13.
- the top of the solvent separation tank 2 and a predetermined position between the pump 11 and the mixer 12 in the line L1 are connected via a line L2.
- the line L2 is provided with a pressure regulating valve V2 and a pressure / flow rate regulating device 14.
- the hydrocarbon solvent (or mixed fluid containing the hydrocarbon solvent) having a critical temperature of 90 ° C. or higher separated in the solvent separation tank 2 is adjusted to a predetermined pressure and flow rate and transferred to the line L1. It is possible.
- An example of the pressure / flow rate adjusting device 14 is a booster.
- the line L2 is connected to a line L3 for introducing a hydrocarbon solvent having a critical temperature of 90 ° C. or more as a makeup gas.
- a raw material containing an aliphatic compound produced by algae is used together with a hydrocarbon solvent (or a mixed fluid containing the hydrocarbon solvent) having a critical temperature of 90 ° C. or more from the line L2.
- the mixture is continuously supplied from the line L1 to the aliphatic compound extraction / separation tank 1, and this mixture is retained in the aliphatic compound extraction / separation tank 1 for a certain period of time.
- the temperature and pressure are adjusted above the critical temperature of the hydrocarbon solvent so that the solubility of the aliphatic compound in 100 g of the hydrocarbon solvent is 15 g or less, and the mixture is held in the aliphatic compound extraction / separation tank 1.
- a method of adjusting the temperature and pressure a method of adjusting the temperature and pressure of the hydrocarbon solvent (or a mixed fluid containing the hydrocarbon solvent) transferred from the solvent separation tank 2 by the pressure / flow rate adjusting device 14, makeup Examples thereof include a method of adjusting the temperature and pressure of the hydrocarbon solvent introduced from the line L2 as gas, a method of adjusting the pressure with the pressure adjusting valve V1, and a method of adjusting the temperature of the mixture with the temperature adjusting device 13.
- One of the above methods may be used alone, or two or more may be used in combination.
- the soluble component of the aliphatic compound in the hydrocarbon solvent and the mixture of the hydrocarbon solvent and the insoluble component of the aliphatic compound in the hydrocarbon solvent (residue ).
- the mixture of the soluble component and the hydrocarbon solvent is transferred to the solvent separation tank 2 through a line L4 connected to the top of the aliphatic compound extraction / separation tank 1.
- a line L5 having a valve V3 is connected to the bottom of the aliphatic compound extraction / separation tank 1, and the other end of the line L5 is led to a recovery container 15.
- the insoluble matter separated in the aliphatic compound extraction / separation tank 1 is transferred to the recovery container 15 through the line L5.
- a small amount of the hydrocarbon solvent can be recovered together when recovering the insoluble matter, but the hydrocarbon solvent may be recovered from the recovery container 15 and reused.
- the soluble component of the aliphatic compound in the hydrocarbon solvent and the mixture of the hydrocarbon solvent are further separated into the aliphatic compound (purified aliphatic compound) and the hydrocarbon solvent by gravity sedimentation separation in the solvent separation tank 2. .
- This separation operation is an operation of adjusting the temperature and / or pressure above the critical temperature of the hydrocarbon solvent so that the solubility of the aliphatic compound in the hydrocarbon solvent becomes substantially zero. Since this separation operation is a gravity sedimentation separation operation that does not involve a phase change, latent heat of vaporization is unnecessary, and sensible heat recovery is possible, which is useful in terms of energy saving.
- a method for lowering the solubility a method in which the pressure in the solvent separation tank 2 is made lower than the pressure in the aliphatic compound extraction / separation tank 1 by adjusting the valve V2, a heating device is provided in the line L4, and the solvent separation tank 2
- the method of making temperature of this higher than the temperature in the aliphatic compound extraction separation tank 1 etc. are mentioned. While the pressure of the solvent separation tank 2 may be made somewhat low, the temperature in the solvent separation tank 2 may be made somewhat high.
- a heating apparatus provided in the line L4 a heat exchanger can be mentioned, for example. In this case, the line L2 may be led to a heat exchanger, and the hydrocarbon solvent from the solvent separation tank 2 may be used as a heat source.
- a line L6 having a valve V4 is connected to the bottom of the solvent separation tank 2, and the other end of the line L6 is led to the recovery container 16.
- the purified aliphatic compound separated in the solvent separation tank 2 is transferred to the recovery container 16 through a line L6 connected to the bottom of the solvent separation tank 2.
- the purified aliphatic compound can be recovered together with a small amount of the hydrocarbon solvent, but the hydrocarbon solvent may be recovered from the recovery container 16 and reused.
- the separated hydrocarbon solvent is transferred to the line L1 through the line L2 connected to the top of the solvent separation tank 2.
- the purified aliphatic compound is transferred from the recovery vessel 16 to the hydroprocessing reactor 3 through the line L7.
- the line L7 is provided with a valve V5, a hydrogen introduction line L8, and a heating device 17 from the upstream side, and the other end of the line L7 is led to the top of the hydrotreating reactor 3.
- the purified aliphatic compound is mixed with hydrogen from the line L8, heated to a predetermined temperature by the heating device 17, and then supplied to the hydroprocessing reactor 3 to perform hydrogenation with a catalyst. .
- a branch line L9 is provided in the line L7.
- One end of the branch line L9 is connected to the upstream side of the valve V5 of the line L7, and the other end is connected between the valve V5 of the line L7 and the connecting portion of the hydrogen introduction line L8.
- the branch line L9 is provided with a valve V6 and an intermediate tank 18 in this order from the upstream side.
- the purified aliphatic compound as the raw material for the hydroprocessing can be temporarily stored in the intermediate tank 20, and the purified fat for the hydroprocessing step can be stored.
- the supply of the group compounds can be stabilized.
- a line L10 is connected to the bottom of the hydrotreating reactor 3, and the hydrocarbon fuel produced by the hydrotreating is recovered from the line L10.
- the present invention is not limited to the above embodiment.
- the example in which the first process and the second process are continuously performed using the manufacturing apparatus illustrated in FIG. 1 has been described. However, these processes may not be performed continuously.
- lines L6 and L7 may be directly connected without providing the collection container 16.
- the hydrotreating reactor 3 may be in a different location from the aliphatic compound extraction / separation tank 1 and the solvent separation tank 2, and has a transport process between the first process and the second process. It may be.
- the intermediate tank 18 can be used as a raw material (receiving) tank.
- This extract was analyzed by a GC-MS method and an NMR method, and it was confirmed that this extract was a wax ester containing myristyl myristate as a main component. Moreover, content of the oxygen atom contained in this extract was 8.1 mass%. As a result of separately measuring the solubility of this extract in hexane at 55 ° C., it was 42 g per 100 g of hexane. That is, the above solvent extraction is performed under this solubility.
- this extract is referred to as hexane extract oil.
- the hexane extract oil remained in the pressure vessel after the propane was extracted, so that the propane extracted from the pressure vessel was the propane dissolved in the saturated hexane extract oil at each temperature. It was judged.
- the propane was volatilized from the propane in which this saturated hexane extract oil was dissolved, and the dissolved hexane extract oil was recovered and weighed, and the solubility of the hexane extract oil at that temperature was calculated as the mass with respect to 100 g of propane.
- propane is newly insoluble in propane in the above propane extraction, and propane is newly added to the hexane extracted oil remaining in the pressure vessel after the propane is discharged. was recovered as described above.
- Table 2 shows the measurement results of the solubility of hexane extract oil in propane at each temperature. From the results shown in Table 2, it can be seen that the solubility varies greatly between 110 ° C. and 120 ° C.
- the dropping was terminated at the point when the pH of the mixed solution reached 7.0, and the resulting slurry-like product was filtered through a filter to obtain a cake-like slurry.
- This cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours.
- the slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product.
- the obtained kneaded product was extruded into a cylindrical shape having a diameter of about 1.5 mm by an extruder and cut into a length of about 3 mm, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. . 50 g of the obtained shaped carrier was put into an eggplant-shaped flask and 17.3 g of molybdenum trioxide, 13.2 g of nickel (II) nitrate hexahydrate, and 3.9 g of phosphoric acid (concentration 85%) while degassing with a rotary evaporator.
- dimethyl sulfide was added to the raw material oil so that the sulfur content relative to the raw material oil (sulfur atom conversion) was 10 ppm by mass.
- the treatment conditions were a hydrogen pressure of 6.0 MPa, a liquid space velocity of 1.0 h ⁇ 1 , and a hydrogen / oil ratio of 510 NL / L.
- the processing temperature is adjusted so that the content of oxygen atoms in the produced oil is 0.5% by mass or less necessary for ensuring the quality of the fuel oil, and is 280 ° C. at the start of the processing based on the result of preliminary examination. did.
- catalyst degradation rate index The rate of increase in the reaction temperature per day necessary for maintaining the oxygen atom content in the product oil at 0.5% by mass or less is used as an index (referred to as “catalyst degradation rate index”). In terms of representation, it was 11.2 ° C./day.
- Comparative Example 2 In place of the hexane extract oil of Comparative Example 1, the condition shown in Table 1 above, where the solubility of hexane extract oil in propane under a pressure of 6 MPa is 26.2 g per 100 g of propane (temperature 110 ° C.) Thus, hydrodeoxygenation treatment was performed by the same operation as in Comparative Example 1 except that the propane-soluble component obtained by repeating propane extraction until the recovery rate reached 90% or more was used. As in Comparative Example 1, the catalyst was significantly deteriorated, and the catalyst deterioration rate index was 10.4 ° C./day.
- Example 1 In place of the hexane extract oil of Comparative Example 1, the condition that the solubility of hexane extract oil in propane under a pressure of 6 MPa shown in Table 1 is 13.7 g per 100 g of propane (temperature: 111 ° C.) Thus, hydrodeoxygenation treatment was performed by the same operation as in Comparative Example 1 except that the propane-soluble component obtained by repeating propane extraction until the recovery rate reached 90% or more was used. Compared with comparative example 1 and comparative example 2, catalyst deterioration was relieved and the catalyst deterioration rate index was 0.7 ° C./day.
- Example 2 A condition (temperature 112 ° C.) in which the solubility of hexane extracted oil in propane under a pressure of 6 MPa shown in Table 1 above is 8.0 g per 100 g of propane instead of the hexane extracted oil of Comparative Example 1
- the same operation as in Comparative Example 1 was performed except that the propane-soluble component obtained by repeating propane extraction until the recovery rate was 90% or more was used.
- the catalyst deterioration was further alleviated, and the catalyst deterioration rate index was 0.5 ° C./day.
- Example 3 In place of the hexane extract oil of Comparative Example 1, the conditions shown in Table 1 above, where the solubility of hexane extract oil in propane under a pressure of 6 MPa is 5.5 g per 100 g of propane (temperature: 114 ° C.) Thus, hydrodeoxygenation treatment was performed by the same operation as in Comparative Example 1 except that the propane-soluble component obtained by repeating propane extraction until the recovery rate reached 90% or more was used. The catalyst deterioration was further alleviated, and the catalyst deterioration rate index was 0.3 ° C./day.
- Table 4 summarizes the results of the above comparative examples and examples. Table 4 also shows the hexane extract oil subjected to hydrodeoxygenation treatment and the impurity concentration in the propane-soluble component obtained by propane extraction under each condition. From the results shown in Table 4, according to the method of the present invention, the catalyst degradation rate index is greatly improved, and high-quality fuel can be stably produced from aliphatic compounds produced by algae. I understand.
- the present invention it is possible to stably produce a high quality hydrocarbon fuel commercially from an aliphatic compound produced by algae. Therefore, the present invention is very useful in producing hydrocarbon fuel from biomass feedstock.
- SYMBOLS 1 Aliphatic compound extraction separation tank, 2 ... Solvent separation tank, 3 ... Hydroprocessing reactor, 11 ... Pump, 12 ... Mixing device, 13, 17 ... Heating device , 14 ... pressure / flow rate adjusting device, 15, 16 ... recovery container, 18 ... intermediate tank, L1-L10 ... line, V1-V5 ... valve.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Analytical Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Description
すなわち、まず、ヘキサンや酢酸エチル等の脂肪族化合物の溶解度が高い溶剤を用いる従来の溶剤抽出方法においては、回収された脂肪族化合物中にマグネシウム(Mg)、ナトリウム(Na)等の金属分が不純物として混入してしまう。これらの金属分は藻類に由来するものと考えられる。そして、このような金属分を含んだ脂肪族化合物を水素化処理工程に供すると、金属分によって触媒が被毒され、触媒が急速に失活してしまうものと考えられる。
これに対して本発明の炭化水素燃料の製造方法においては、藻類によって産生された脂肪族化合物と、超臨界状態にある臨界温度が90℃以上の炭化水素溶媒と、を含む混合物を、脂肪族化合物の炭化水素溶媒への溶解度が炭化水素溶媒100g当たり15g以下となるように、温度及び圧力を調整して保持した後、脂肪族化合物の炭化水素溶媒への可溶分を回収することによって、回収された脂肪族化合物への金属分の混入を十分に抑制することができる。そして、そのようにして回収された脂肪族化合物を水素化処理工程に供することによって、金属分による触媒の被毒及び失活を十分に抑制することができるものと推察される。
処理する第2の工程と、を備える。
なお、前記担体は、成型性及び機械的強度を向上させる目的で、アルミナ、シリカ、チタニア、マグネシア等のバインダを含有してもよい。
ユーグレナの培養を成書「ユーグレナ 生理と生化学」、学会出版センター(1989)付録の記載の方法に従って実施した。E.Gracilis Z株を用いて面積1.2m2のプールを利用して、Cramer-Myers培地の下で、屋外で太陽光により7日間培養を行った。その後、同書114ページの記載に従って丸1日嫌気処理を行い、更にこれを150℃で乾燥することによりユーグレナの乾燥粉体を得た。同じ操作を繰り返すことにより、嫌気処理済みのユーグレナ乾燥粉体を1700g回収した。
藻類からの脂肪族化合物の抽出に最も幅広く使用されているヘキサンを溶媒として使用して抽出を行なった。容量20Lのフラスコに1650gの上記乾燥粉体とヘキサン10Lを仕込み、得られた懸濁液を常圧下、55℃で1時間加熱・撹拌した後に、濾過することによりヘキサン溶液を回収した。
このヘキサン溶液から、エバポレータを用いて(湯浴温度50℃)ヘキサンを留去することによって、藻体からの抽出物を乾燥藻体に対して27.5質量%の割合で得た。この抽出物をGC-MS法及びNMR法により分析し、この抽出物がミリスチン酸ミリスチルを主成分とするワックスエステルであることを確認した。またこの抽出物中に含まれる酸素原子の含有量は8.1質量%であった。
この抽出物の55℃におけるヘキサンへの溶解度を別途測定した結果、ヘキサン100g当たり42gであった。すなわち、この溶解度の下で、上記の溶剤抽出を実施したことになる。以下この抽出物をヘキサン抽出油と呼ぶ。
内容積1Lの圧力容器を用いて、各条件において上記ヘキサン抽出油のプロパンへの溶解度の測定及び上記ヘキサン抽出油のプロパンによる抽出を実施した。
上記測定及び抽出においては、所定温度に制御された容器内にヘキサン抽出油を仕込み、そこにプロパンを供給し、圧力を6MPaの状態で1h保持し、ヘキサン抽出油をプロパンに溶解させた(プロパン抽出)。その後、ヘキサン抽出油の一部が溶解した状態のプロパンを全量容器から抜き出した。各温度において、プロパンを抜き出した後の圧力容器中にはヘキサン抽出油が残留していたので、圧力容器から抜き出されたのは各温度における飽和濃度のヘキサン抽出油を溶解したプロパンであると判断した。
この飽和濃度のヘキサン抽出油が溶解したプロパンからプロパンを揮発させ、溶解していたヘキサン抽出油を回収して秤量し、プロパン100gに対する質量として、当該温度におけるヘキサン抽出油の溶解度を算出した。
また、各温度において、上記プロパン抽出においてプロパンに不溶であり、プロパン排出後に圧力容器中に残留していたヘキサン抽出油に新たにプロパンを添加して、ヘキサン抽出油のプロパン抽出及びプロパン可溶分の回収を上記と同様にして行なった。そして、プロパン抽出により回収されたヘキサン抽出油の合計の質量の圧力容器に仕込んだヘキサン抽出油の質量に対する割合(回収率)が90%以上となるまでこの操作を繰り返し実施した。
各温度における、ヘキサン抽出油のプロパンに対する溶解度の測定結果を表2に示す。表2に示した結果から、温度が110℃から120℃の間で大きく溶解度が変化することが分かる。
濃度5質量%のアルミン酸ナトリウム水溶液3000gに水ガラス3号18.0gを加え、65℃に保温した容器に入れた。他方、65℃に保温した別の容器において濃度2.5質量%の硫酸アルミニウム水溶液3000gにリン酸(濃度85%)6.0gを加えた溶液を調製し、これに前述のアルミン酸ナトリウムを含む水溶液を滴下した。混合溶液のpHが7.0になる時点を終点として滴下を終了し、得られたスラリー状の生成物をフィルターに通して濾取し、ケーキ状のスラリーを得た。
このケーキ状のスラリーを還流冷却器を取り付けた容器に移し、蒸留水150mlと27%アンモニア水溶液10gを加え、75℃で20時間加熱・攪拌した。該スラリーを混練装置に入れ、80℃以上に加熱し水分を除去しながら混練し、粘土状の混練物を得た。得られた混練物を押出成形機によって直径約1.5mmの円筒状の形状に押し出して長さ約3mmに切断し、110℃で1時間乾燥した後550℃で焼成し、成形担体を得た。
得られた成形担体50gをナス型フラスコに入れ、ロータリーエバポレーターで脱気しながら三酸化モリブデン17.3g、硝酸ニッケル(II)6水和物13.2g、リン酸(濃度85%)3.9g及びリンゴ酸4.0gを含む含浸水溶液をフラスコ内に注入して含浸を行なった。含浸した試料は120℃で1時間乾燥した後、550℃で焼成し、触媒を得た。触媒の物性を表3に示す。
上記触媒(10ml)を充填した反応管を固定床流通式反応装置に向流に取り付けた。その後、ジメチルジサルファイドを加えた直留軽油(硫黄分3質量%)を用いて触媒層平均温度300℃、水素分圧6MPa、液空間速度1h-1、水素/油比200NL/L(「NL」は0℃、大気圧における水素ガスの容積)の条件下で、4時間触媒の予備硫化を行った。
予備硫化後、前出のヘキサン抽出油(プロパン抽出を行なっていない)を原料油として水素化脱酸素処理を行った。なおその際、原料油に対する硫黄分含有量(硫黄原子換算)が10質量ppmになるようにジメチルサルファイドを原料油に添加した。処理の条件は、水素圧力を6.0MPa、液空間速度を1.0h-1、水素/油比を510NL/Lとした。また、処理温度は生成油中の酸素原子の含有量が燃料油品質を確保するために必要な0.5質量%以下となるよう調整し、予備検討の結果を基に処理開始時には280℃とした。その後触媒の劣化(活性低下)が著しいため、前記生成油中の酸素原子の含有量を維持するために、処理温度を経時的に大きな幅で上げざるを得なかった。触媒の劣化速度を、生成油中の酸素原子の含有量を0.5質量%以下に維持するために必要な1日当りの反応温度の上昇幅を指標(「触媒劣化速度指標」という。)として表すと、11.2℃/日となった。
比較例1のヘキサン抽出油に代えて、前出の表1に示した、圧力6MPaの下でのヘキサン抽出油のプロパンへの溶解度が、プロパン100g当たり26.2gとなる条件(温度110℃)で、回収率が90%以上となるまでプロパン抽出を繰り返して得られたプロパン可溶分を用いたこと以外は、比較例1と同様の操作により水素化脱酸素処理を行った。比較例1と同様に触媒の劣化が著しく、触媒劣化速度指標は10.4℃/日となった。
比較例1のヘキサン抽出油に代えて、前出の表1に示した、圧力6MPaの下でのヘキサン抽出油のプロパンへの溶解度が、プロパン100g当たり13.7gとなる条件(温度111℃)で、回収率が90%以上となるまでプロパン抽出を繰り返して得られたプロパン可溶分を用いたこと以外は、比較例1と同様の操作により水素化脱酸素処理を行った。比較例1及び比較例2に比べて触媒劣化が緩和され、触媒劣化速度指標は0.7℃/日となった。
比較例1のヘキサン抽出油に代えて、前出の表1に示した、圧力6MPaの下でのヘキサン抽出油のプロパンへの溶解度が、プロパン100g当たり8.0gとなる条件(温度112℃)で、回収率が90%以上となるまでプロパン抽出を繰り返して得られたプロパン可溶分を用いたこと以外は比較例1と同様の操作を行った。触媒劣化がさらに緩和され、触媒劣化速度指標は0.5℃/日となった。
比較例1のヘキサン抽出油に代えて、前出の表1に示した、圧力6MPaの下でのヘキサン抽出油のプロパンへの溶解度が、プロパン100g当たり5.5gとなる条件(温度114℃)で、回収率が90%以上となるまでプロパン抽出を繰り返して得られたプロパン可溶分を用いたこと以外は、比較例1と同様の操作により水素化脱酸素処理を行った。触媒劣化が一層緩和され、触媒劣化速度指標は0.3℃/日となった。
Claims (1)
- 藻類によって産生された脂肪族化合物と、超臨界状態にある臨界温度が90℃以上の炭化水素溶媒とを含有する混合物を、前記炭化水素溶媒100gに対する前記脂肪族化合物の溶解度が15g以下となるように、温度及び圧力を調整して保持した後、前記脂肪族化合物の前記炭化水素溶媒への可溶分を回収する第1の工程と、
前記第1の工程で回収された可溶分を、触媒を用いて水素化処理する第2の工程と、
を備える炭化水素燃料の製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2012226064A AU2012226064A1 (en) | 2011-03-07 | 2012-01-19 | Hydrocarbon fuel production method |
US14/003,322 US20140051899A1 (en) | 2011-03-07 | 2012-01-19 | Hydrocarbon fuel production method |
KR1020137024049A KR20140020906A (ko) | 2011-03-07 | 2012-01-19 | 탄화수소 연료의 제조방법 |
EP12755377.4A EP2684937A4 (en) | 2011-03-07 | 2012-01-19 | PROCESS FOR PRODUCING HYDROCARBON FUEL |
CN2012800120271A CN103415593A (zh) | 2011-03-07 | 2012-01-19 | 烃燃料的制造方法 |
SG2013066154A SG193273A1 (en) | 2011-03-07 | 2012-01-19 | Hydrocarbon fuel production method |
BR112013022637A BR112013022637A2 (pt) | 2011-03-07 | 2012-01-19 | método de produção de combustível de hidrocarboneto |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011049282A JP5807947B2 (ja) | 2011-03-07 | 2011-03-07 | 炭化水素燃料の製造方法 |
JP2011-049282 | 2011-03-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012120926A1 true WO2012120926A1 (ja) | 2012-09-13 |
Family
ID=46797897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/051126 WO2012120926A1 (ja) | 2011-03-07 | 2012-01-19 | 炭化水素燃料の製造方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US20140051899A1 (ja) |
EP (1) | EP2684937A4 (ja) |
JP (1) | JP5807947B2 (ja) |
KR (1) | KR20140020906A (ja) |
CN (1) | CN103415593A (ja) |
AU (1) | AU2012226064A1 (ja) |
BR (1) | BR112013022637A2 (ja) |
MY (1) | MY162960A (ja) |
SG (1) | SG193273A1 (ja) |
WO (1) | WO2012120926A1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8192628B2 (en) * | 2010-07-26 | 2012-06-05 | Sapphire Energy, Inc. | Process for the recovery of oleaginous compounds from biomass |
JP6332689B2 (ja) * | 2014-09-09 | 2018-05-30 | 国立研究開発法人産業技術総合研究所 | 炭化水素の製造方法 |
US20160096782A1 (en) * | 2014-10-01 | 2016-04-07 | Uop Llc | Methods and apparatuses for processing bio-derived normal nonane |
JP6536369B2 (ja) * | 2015-11-12 | 2019-07-03 | 株式会社デンソー | 潤滑性推定装置および燃料供給制御装置 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09803A (ja) * | 1995-06-19 | 1997-01-07 | Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko | ボツリオコッカス属に属する微細藻類から炭化水素類を抽出する方法 |
JP2007308564A (ja) | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | 水素化精製方法 |
JP2007308565A (ja) | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | 水素化精製方法 |
JP2010111865A (ja) * | 2008-10-10 | 2010-05-20 | Univ Of Tokyo | 炭化水素の製造方法及び炭化水素製造システム |
JP2010121071A (ja) | 2008-11-20 | 2010-06-03 | Nippon Oil Corp | 航空燃料油基材および航空燃料油組成物 |
WO2011025002A1 (ja) * | 2009-08-31 | 2011-03-03 | Jx日鉱日石エネルギー株式会社 | 航空燃料油基材の製造方法及び航空燃料油組成物 |
JP2011246605A (ja) * | 2010-05-26 | 2011-12-08 | Hitachi Plant Technologies Ltd | バイオ燃料製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06311882A (ja) * | 1993-04-30 | 1994-11-08 | Kawasaki Steel Corp | 海洋性微細藻類の脱臭方法 |
DE10155281A1 (de) * | 2001-11-08 | 2003-06-05 | Solvent Innovation Gmbh | Verfahren zur Entfernung polarisierbarer Verunreinigungen aus Kohlenwasserstoffen und Kohlenwasserstoffgemischen durch Extraktion mit ionischen Flüssigkeiten |
NZ547429A (en) * | 2006-05-24 | 2009-09-25 | Ind Res Ltd | Extraction of highly unsaturated lipids with liquid dimethyl ether |
CN101144047A (zh) * | 2006-09-15 | 2008-03-19 | 吴膺丰 | 一种提取植物性油脂的方法 |
US20100028962A1 (en) * | 2006-09-18 | 2010-02-04 | Qiang Hu | Algal Medium Chain Length Fatty Acids and Hydrocarbons |
US7977076B2 (en) * | 2006-12-29 | 2011-07-12 | Genifuel Corporation | Integrated processes and systems for production of biofuels using algae |
US8003834B2 (en) * | 2007-09-20 | 2011-08-23 | Uop Llc | Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks |
EP2222817A4 (en) * | 2007-12-21 | 2013-10-23 | Uop Llc | MANUFACTURE OF A FLYING FUEL FROM RENEWABLE RAW MATERIAL |
JP2009191008A (ja) * | 2008-02-14 | 2009-08-27 | South Product:Kk | 褐藻類由来機能性成分の抽出方法 |
US7888540B2 (en) * | 2008-04-11 | 2011-02-15 | General Electric Company | Integrated system and method for producing fuel composition from biomass |
CN101613618B (zh) * | 2008-06-27 | 2013-03-27 | 新奥科技发展有限公司 | 一种以微藻油脂为原料制备生物柴油的方法 |
CN101474493A (zh) * | 2008-12-05 | 2009-07-08 | 符文飙 | 一种混合溶剂低压流体临界提取方法 |
CN101747924B (zh) * | 2008-12-19 | 2013-08-28 | 普罗米绿色能源(深圳)有限公司 | 以藻类植物为原料生产生物柴油的方法 |
US20110016776A1 (en) * | 2009-07-22 | 2011-01-27 | Joshi Chandrashekhar H | Fuel Composition Derived from Biodiesel |
-
2011
- 2011-03-07 JP JP2011049282A patent/JP5807947B2/ja active Active
-
2012
- 2012-01-19 AU AU2012226064A patent/AU2012226064A1/en not_active Abandoned
- 2012-01-19 CN CN2012800120271A patent/CN103415593A/zh active Pending
- 2012-01-19 SG SG2013066154A patent/SG193273A1/en unknown
- 2012-01-19 WO PCT/JP2012/051126 patent/WO2012120926A1/ja active Application Filing
- 2012-01-19 BR BR112013022637A patent/BR112013022637A2/pt not_active IP Right Cessation
- 2012-01-19 KR KR1020137024049A patent/KR20140020906A/ko not_active Application Discontinuation
- 2012-01-19 EP EP12755377.4A patent/EP2684937A4/en not_active Withdrawn
- 2012-01-19 US US14/003,322 patent/US20140051899A1/en not_active Abandoned
- 2012-01-19 MY MYPI2013701575A patent/MY162960A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09803A (ja) * | 1995-06-19 | 1997-01-07 | Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko | ボツリオコッカス属に属する微細藻類から炭化水素類を抽出する方法 |
JP2007308564A (ja) | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | 水素化精製方法 |
JP2007308565A (ja) | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | 水素化精製方法 |
JP2010111865A (ja) * | 2008-10-10 | 2010-05-20 | Univ Of Tokyo | 炭化水素の製造方法及び炭化水素製造システム |
JP2010121071A (ja) | 2008-11-20 | 2010-06-03 | Nippon Oil Corp | 航空燃料油基材および航空燃料油組成物 |
WO2011025002A1 (ja) * | 2009-08-31 | 2011-03-03 | Jx日鉱日石エネルギー株式会社 | 航空燃料油基材の製造方法及び航空燃料油組成物 |
JP2011246605A (ja) * | 2010-05-26 | 2011-12-08 | Hitachi Plant Technologies Ltd | バイオ燃料製造方法 |
Non-Patent Citations (4)
Title |
---|
"Use", 1992, CO., LTD., pages: 64 - 74 |
"Yugurena Seiri To Seikagaku", 1989, GAKKAI SHUPPAN SENTA |
MASAKI OTA, pages 96 - 100 |
See also references of EP2684937A4 |
Also Published As
Publication number | Publication date |
---|---|
AU2012226064A1 (en) | 2013-10-10 |
JP2012184356A (ja) | 2012-09-27 |
US20140051899A1 (en) | 2014-02-20 |
KR20140020906A (ko) | 2014-02-19 |
EP2684937A4 (en) | 2014-07-30 |
BR112013022637A2 (pt) | 2016-12-06 |
SG193273A1 (en) | 2013-10-30 |
CN103415593A (zh) | 2013-11-27 |
JP5807947B2 (ja) | 2015-11-10 |
MY162960A (en) | 2017-07-31 |
EP2684937A1 (en) | 2014-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2084245B1 (en) | Process for producing hydrocarbon fractions from mixtures of a biological origin | |
JP5857095B2 (ja) | モリブデンベースの触媒を用いることにより再生可能な起源の流出物を優れた品質の燃料に転化する方法 | |
US8552235B2 (en) | Process for hydrodeoxygenation of feeds derived from renewable sources with limited decarboxylation conversion using a catalyst based on nickel and molybdenum | |
JP4878824B2 (ja) | 環境低負荷型燃料の製造方法および環境低負荷型燃料 | |
RU2495082C2 (ru) | Способ и катализатор гидропереработки | |
KR101301459B1 (ko) | 수소화 정제방법 | |
JP5317644B2 (ja) | 航空燃料油基材の製造方法 | |
JP2010509472A5 (ja) | ||
EP2356197B1 (en) | Process for the production of hydrocarbon composition useful as fuel and combustible obtained from oil components and a biological component | |
ITMI20082214A1 (it) | Processo per la produzione di idrocarburi, utili per autotrazione, da miscele di origine biologica | |
JP5807947B2 (ja) | 炭化水素燃料の製造方法 | |
JP2007308564A (ja) | 水素化精製方法 | |
KR101452793B1 (ko) | 수소화 정제방법 | |
JP5022117B2 (ja) | 炭化水素油の製造方法 | |
JP5189740B2 (ja) | 水素化精製方法 | |
JP2009019175A (ja) | 炭化水素油の製造方法 | |
EP2781579A1 (en) | Method for producing fuel oil | |
CN109294613B (zh) | 一种油脂类原料制备烃燃料的方法 | |
ES2692174T3 (es) | Proceso para preparar una composición de hidrocarburo útil como carburante o combustible | |
JP2018095723A (ja) | ディーゼル燃料基材、ディーゼル燃料組成物、ディーゼル燃料基材の製造方法およびディーゼル燃料組成物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12755377 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137024049 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2012755377 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012755377 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2012226064 Country of ref document: AU Date of ref document: 20120119 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14003322 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013022637 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112013022637 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130904 |